High temperature isomerization of (e)-1-chloro-3,3,3-trifluoropropene to (z)-1-chloro-3,3,3-trifluoropropene

ABSTRACT

Disclosed are processes for a high temperature isomerization reaction converting (E)-1-chloro-3,3,3-trifluoropropene to (Z)-1-chloro-3,3,3-trifluoropropene. In certain aspects of the invention, such a process includes contacting a feed stream with a heated surface, where the feed stream includes (E)-1-chloro-3,3,3-trifluoropropene or mixture of (E)-1-chloro-3,3,3-trifluoropropene with (Z)-1-chloro-3,3,3-trifluoropropene. The resulting product stream includes (Z)-1-chloro-3,3,3-trifluoropropene and (E)-1-chloro-3,3,3-trifluoropropene, where the ratio of (Z) isomer to (E) isomer in the product stream is higher than the ratio feed stream. The (E) and (Z) isomers in the product stream may be separated from one another.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a division of U.S. application Ser. No.14/886,628, filed Oct. 19, 2015, which application is a division of U.S.application Ser. No. 14/204,637, filed Mar. 11, 2014, (now U.S. Pat. No.9,162,947, issued Oct. 20, 2015), which application claims priority toU.S. Provisional Application Ser. No. 61/789,312, filed Mar. 15, 2013,the contents of which are incorporated herein by reference in theirentirety.

FIELD OF THE INVENTION

The present invention relates to processes for the production of1-chloro-3,3,3-trifluoropropene (1233zd) and, in certain aspects, to theconversion of a 1-chloro-3,3,3-trifluoropropene (E) isomer to a1-chloro-3,3,3-trifluoropropene (Z) isomer.

BACKGROUND

Many existing CFCs are known to be ozone-depleting compounds. Thus, theuse of these compounds has been curtailed in favor of chemicals that aremore commercially acceptable. In some cases, alternate CFC compoundshave been found to be both effective and more environmentally friendly.As one example, 1-chloro-3,3,3-trifluoropropene (hereinafter “1233zd”)has been found to have a wide variety of uses, for example as a heattransfer agent, as a foaming agent, and as a solvent, among other uses.U.S. Patent Publication Nos. 2008/0098755, entitled “Heat TransferMethods Using Heat Transfer Compositions ContainingTrifluoromonochloropropene,” and 2008/0207788, entitled “Foaming Agents,Foamable Compositions, Foams and Articles Containing FluorineSubstituted Halogens, and Methods of Making the Same” and U.S. Pat. No.6,362,383, entitled “Hydro-Fluorination of Chlorinated Hydrocarbons” alldisclose examples of such uses. The contents of each of these referencesare incorporated herein by reference in their entirety.

1233zd may be produced by any one of a number of different methods. Forexample, U.S. Pat. No. 7,829,747, entitled “Process forDehydrofluorination of 3-chloro-1,1,13-tetrafluoropropane to1-chloro-3,3,3-trifluoropropene”; U.S. Pat. No. 5,710,352, entitled“Vapor Phase Process for Making 1,1,1,3,3-pentafluoropropane and1-chloro-3,3,3-trifluoropropene;” U.S. Pat. No. 6,111,150, entitled“Method for Producing 1,1,1,3,3-pentafluoropropane;” and U.S. Pat. No.6,844,475, entitled “Low Temperature Production of1-chloro-3,3,3-trifluoropropene (HCFC-1233zd)” all describe severalmethods for making 1233zd. The contents of each of these referencesincorporated by reference herein in their entirety.

1233zd has two isomers, (E) and (Z), with different physical properties.As one example of the different properties between the two isomers,1233zd(Z) has a boiling point of approximately 38° C., whereas 1233zd(E)has a boiling point of approximately 19° C. In some applications, it isdesirable to use either pure 1233zd(E), pure 1233zd(Z), a particularblend of the (Z) and (E) isomers, or a particular blend of one or bothof the 1233zd isomers and another compound in order to control theproperties of the solution. For example, in some solvent applications,it is desirable to have a relatively high boiling point. In some suchapplications, pure 1233zd(Z) may have more desirable physical properties(e.g., a higher boiling point) than either pure 1233zd(E) or mixtures ofthe two 1233zd isomers.

In some prior art isomerization reactions, reagents (defined herein asany chemically reactive materials, i.e., not the 1233zd itself or thevarious catalysts described herein) are used to facilitate theisomerization of the 1233zd. For example, in one prior art isomerizationreaction bromine is added to 1233zd(E) in order to isomerize 1233zd. Insome embodiments of the present invention, the isomerization reaction isreagent-free, or it does not require the use of any reagents. As furtherdescribed below, in some embodiments the absence of reagents facilitatesthe production of pure 1233zd, and more particularly may facilitate theproduction of pure 1233zd(Z) and pure 1233zd(E).

Isomerization of 1233zd(E) to form 1233zd(Z) is disclosed in the U.S.Pa. No. 8,217,208, the contents of which are incorporated herein byreference in its entirety, which provides a low temperatureisomerization process. The deficiency of this process, however, is thatit results in low selectivity to 1233zd(Z) and the formation ofsignificant amounts of by-products (see, for example, table 3 of example4 exhibiting selectivity to 1233zd(Z) of about 80%).

Accordingly, there exists a need for processes that selectively provideone or both of the commercially desirable isomers of 1233zd,particularly for the conversion of 1233zd(E) to form 1233zd(Z) withincreased yield and selectivity.

SUMMARY

The present invention, in certain aspects, relates to a high temperatureprocess for converting a 1233zd(E) isomer to a 1233zd(Z) isomer. Incertain preferred aspects, such a method includes providing a feedstream comprising, consisting essentially of, or consisting of(E)1-chloro-3,3,3-trifluoropropene or a mixture of(E)1-chloro-3,3,3-trifluoropropene and(Z)1-chloro-3,3,3-trifluoropropene. In further aspects, the lattermixture of the (E) and (Z) isomers contains less than about 5 wt %(Z)1-chloro-3,3,3-trifluoropropene, based on the total weight of thefeed stream.

The feed stream is contacted with a heated surface that is maintained ata temperature of greater than 400° C. for a period of time sufficient toconvert at least a portion of the (E) 1-chloro-3,3,3-trifluoropropene to(Z)1-chloro-3,3,3-trifluoropropene. To this end, it results in a productstream having more (Z) isomer than in the feed stream. In certainaspects, the heated surface is maintained at a temperature from greaterthan 400° C. to about 550° C., in further embodiments from greater than400° C. to about 500° C., in even further embodiments from greater than400° C. to about 475° C., and in even further embodiments from greaterthan 400° C. to about 450° C. The feed stream may be optionallyvaporized before or after contacting the heated surface.

The heated surface may also include an outer packing material, which incertain aspects acts as a catalyst to the reaction. Non-limitingexamples of such packing material include stainless steel, nickel andnickel-based compositions. In certain embodiments, they includenickel-based alloys. Other catalysts may include, but are not limitedto, metal oxides, halogenated metal oxides, Lewis acid metal halides,zero-valent metals, or a mixture or alloy thereof.

The resulting product stream may be distilled to separate the (E) and(Z) isomers from one another. In certain aspects, the product streamcontains more than 5 wt % (Z)1-chloro-3,3,3-trifluoropropene, based onthe total weight of the product stream. In further embodiments, itcontains between about 5 wt % and about 17 wt %(Z)1-chloro-3,3,3-trifluoropropene, based on the total weight of theproduct stream.

Additional embodiments and advantages of the instant invention will bereadily apparent to one of skill in the art based on the additionaldisclosure provided herein.

DETAILED DESCRIPTION

The present invention relates, in part, to a high temperature processfor isomerization of 1233zd(E) to form 1233zd(Z). Applicants to thepresent invention have surprisingly and unexpectedly found the hightemperature process described herein results in improved conversion ofthe 1233zd(E) isomer and improved selectivity for the 1233zd(Z) isomer.In certain aspects, the selectivity for 1233zd(Z) is greater than 80%,greater than 90%, or greater than 95%.

As further described below, in certain embodiments of the presentinvention the feed stream comprises, consists essentially of, orconsists of either 1233zd(E) or a mixture of 1233zd(E) and 1233zd(Z).The feed stream also may contain materials or impurities other than1233zd(Z) or 1233zd(E). In certain non-limiting embodiments, the feedstreams may be substantially free of such impurities. To this end, andin certain non-limiting embodiments, substantially free (at least withrespect to the impurities) means that the impurity level is sufficientlylow such that the impurities do not measurably impact the isomerizationprocess provided herein. In further non-limiting embodiments, the feedstreams may also be substantially free of impurities if they containless than 5 wt %, less than 3 wt %, less than 2 wt %, less than 1.5 wt%, or less than 1 wt % of other compounds, based on the total weight ofthe feed stream. Non-limiting examples of such impurities may includehydrofluorocarbons, hydrochlorocarbons, hydrochlorofluorocarbons,halogenated olefins, or other compounds other than 1233zd. Some of thesecompounds may be byproducts or unreacted compounds from the productionof the 1233zd. While it is preferred in certain embodiments that theimpurities not react or interfere with isomerization process, in certainother embodiments, the impurities or additional materials, if present,may react with the 1233zd or with other compounds within anisomerization reaction, and in the process may affect the yield orpurity of a product stream from the isomerization reaction.

According to certain embodiments of the invention, a method is providedfor converting between the (E) and (Z) isomers of 1233zd, particularlyto conversion the (E) isomer to the (Z) isomer. The method includes anisomerization reaction that has a thermodynamic equilibrium at which anequilibrium ratio of (E) isomer to (Z) isomer is present. As indicatedby the examples described below, the equilibrium ratio may varydepending on certain reaction conditions, including the temperature, thetype and configuration of the reactor vessel, and/or the presence of oneor more catalysts. If the ratio of E to Z isomer is greater than theequilibrium ratio, then at least a portion of the 1233zd(E) is convertedinto 1233zd(Z).

In other embodiments, the method includes controlling the temperature ofa heated surface to greater than 300° C., in certain preferred aspectsto greater than 350° C., and in further preferred aspects to greaterthan 400° C. The heated surface is contacted with a feed streamcomprising, consisting essentially of, or consisting of 1233zd(E) or amixture of (E) and 1233zd(Z). This contacting step may be for any periodof time sufficient to convert at least a portion of the 1233zd(E) to1233zd(Z), thus producing a product stream with a concentration of1233zd(Z) that is higher than that in the feed stream.

In certain embodiments, the heated surface includes the interior surfaceof a reactor vessel. In addition, or in the alternative, the heatedsurface may include an outer surface of a packing material, for examplea packing material that is packed in a reaction vessel. In certainembodiments, the reactor vessel is a continuous-type reactor vessel, forexample a reactor vessel is a plug flow reactor. The feed stream is fedinto the reactor vessel at a rate sufficient to isomerize the desiredamount of 1233zd(E) to 1233zd(Z). The resulting product stream exits thereactor and is available for further purification of E and Z isomers of1233zd. In one example, the reactor vessel is an elongate reactor vessel(e.g., a Stainless Steel, nickel Inconel, or Monel tube or pipe).

In certain embodiments, the reactor vessel may be partially or entirelypacked with packing material, for example with a stainless steelpacking, nickel packing, inconel packing, monel packing, or the like. Incertain embodiments, the relatively large surface area of the packingmaterial may facilitate the conversion reaction between the (E) and (Z)isomers. Support structures that support the packing material may alsobe disposed in or on the reactor vessel. For example, the packingmaterial may be supported by a mesh or other structure that is disposedunder, around, and/or within the packing material. The support structuremay comprise the same material as the packing material (e.g., stainlesssteel, nickel, inconel, monel), nickel, or any other suitable material.

The packing materials may also comprise one or more catalyst materials.Examples of suitable catalysts for the isomerization of 1233zd arezero-valent metals supported on a substrate (activated carbon, metaloxide, metal oxyhalide, metal halide) or unsupported, as well ascombinations of these catalysts. In certain preferred aspects, thepacking materials are adapted to increase selectivity and conversion attemperatures greater than 400° C. and may exhibit catalytic properties.Non-limiting examples of such packing materials include stainless steel,nickel and nickel-containing compositions. In certain preferred aspects,the packing materials include nickel-based alloys. Non-limiting examplesof such nickel-based alloys include, but not limited to, Monel® basedmaterials (including Monel® 400) and Inconel® based materials (includingInconel® 600 and 625).

The feed stream may be fed into the reactor vessel in the vapor phase.Alternately, the feed stream is fed into the reactor vessel in theliquid phase and the temperature of the heated surface within thereactor vessel causes the feed stream to vaporize. Examples of suitabletemperatures for the heated surface within the reactor vessel aregreater than about 250° C., greater than about 300° C., greater thanabout 350° C., or greater than about 400° C. In certain embodiments, thetemperature of the heated surface within the reaction vessel is fromgreater than 400° C. to about 550° C., from greater than 400° C. toabout 500° C., from greater than 400° C. to about 475° C., or fromgreater than 400° C. to about 450° C.

The pressure in the reactor vessel during the isomerization reaction maybe at or slightly above atmospheric pressure, or it may be betweenatmospheric pressure and 300 psi, between atmospheric pressure and 200psi, or between atmospheric pressure and 100 psi. In continuous-typereactor vessels, the feed stream may be fed in at slightly aboveatmospheric pressure or within any of the elevated pressure rangesspecified above, or the feed stream may be fed into the reactor vesselbelow atmospheric pressure and the exit of the reactor vessel may beplaced under vacuum.

In certain embodiments, the feed steam includes a mixture of 1233zd(E)and 1233zd(Z). While the amount of 1233zd(Z) is not necessarily limitingto the present invention and such an isomer may be provided in anyamount, in certain aspects, it is present in an amount of less thanabout 10 wt %, in further aspects in an amount less than 9 wt. %1233zd(Z), and in further embodiments in an amount of less than about 7wt. % of the composition, based on the total weight of the feed stream.In certain embodiments, feed stream is substantially free of 1233zd(Z),which includes compositions having no measurable amount of 1233zd(Z). Infurther non-limiting embodiments, however, the feed steam may besubstantially free of 1233zd(Z) if it contains less than 5 wt %1233zd(Z), less than 3 wt % 1233zd(Z), less than 1 wt. % 1233zd(Z), oris entirely free of 1233zd(Z), based on the total weight of the feedstream.

The feed stream in any of the foregoing amounts is then contacted with aheated surface, particularly within the temperature ranges providedherein for a sufficient or effective amount of time such that thedesired amount of 1233zd(Z) is present in the product stream. In certainnon-limiting aspects, a “sufficient time” or “effective time” means anamount of time where measurable conversion of 1233zd(E) to 1233zd(Z) isdetectable or where the amount of 1233zd(Z) in the resulting productstream is within the desired range, particularly the weight percentageranges provided herein. In certain further aspects of the invention suchtimes may be between 1 second and 15 minutes, in certain preferredaspects between about 10 seconds and 5 minutes.

The amount of 1233zd(Z) in the product stream may be any amount greaterthan the concentration of 1233zd(Z) in the starting or feed stream. Incertain embodiments, this amount is greater than 1%, greater than about5 wt %, greater than about 7 wt %, greater than about 9 wt %, greaterthan about 10 wt %, greater than about 12 wt %, or greater than about 15wt %, based on the total weight of the product stream. In furtherembodiments, the amount of 1233zd(Z) in the product stream may bebetween about 5 wt % and about 20 wt %, between about 5 wt % and about17 wt %, between about 5 wt % and about 15 wt %, between about 5 wt %and about 12 wt %, or about 5 wt %, about 7 wt %, about 9 wt %, about 10wt %, about 12 wt %, or about 15 wt %, based on the total weight of theproduct stream. In certain embodiments, the amount of 1233zd(Z) in theproduct stream corresponds to the equilibrium ratio of 1233zd(Z),whereas in other embodiments the amount of 1233zd(Z) corresponds to lessthan the equilibrium ratio of 1233zd(Z).

In further embodiments, the amount of 1233zd(E) in the product streammay be less than about 95 wt %, less than about 90 wt %, less than about80 wt %, less than about 70 wt %, less than about 60 wt %, based on thetotal weight of the product stream.

In certain alternative embodiments of the invention, the method ofconverting between (E)1-chloro-3,3,3-trifluoropropene and(Z)1-chloro-3,3,3-trifluoropropene, comprises providing a vaporized feedstream comprising, consisting essentially of, or consisting of one orboth isomers of 1-chloro-3,3,3-trifluoropropene. The feed stream has afirst ratio of (E) isomer to (Z) isomer. As discussed herein, atemperature controlled reaction vessel may be used that includes aninterior surface, a first opening, a second opening, a pathway fluidlyconnecting the first and second openings, and a packing materialdisposed in the pathway. The heated surface may include the interiorsurface and the packing material contacting the feed stream with theheated surface that is maintained at a desired temperature. The desiredtemperature may be any of the temperature ranges mentioned herein, incertain preferred embodiments greater than 350° C., in further preferredembodiments greater than 400° C., or as otherwise provided herein. Thefeed stream may be contacted with the heated surface for a period oftime sufficient to convert the feed stream into a product stream havinga second ratio of (E) to (Z) isomer.

Because the methods described above include equilibrium reactions, theproduct streams will comprise a mixture of both isomers of 1233zd.However, because of differing physical properties (e.g., differentboiling points), the two isomers may be separated from one another usinga separation process. For example, the product stream from any of theabove methods may be fed directly into a suitable distillationoperation. In other embodiments, the product stream is fed through anintermediate unit operation prior to being fed into the distillationcolumn or is stored prior to being fed through the distillation column.In certain embodiments, the distillation process yields substantiallypure, or pure, separated product streams of 1233zd(Z) and 1233zd(E).Where only one of the (Z) or (E) separated product streams arecommercially desirable, all or a portion of the undesirable separatedproduct stream may be recycled back into an isomerization process.

In certain embodiments in which the product streams of the above methodscomprises additional compounds other than the isomers of 1233zd, theadditional compounds may have similar properties (e.g., boiling points)to one of the (Z) or (E) isomers that may cause the additional compoundsto be captured in either or both of the (Z) or (E) product streams. Insuch embodiments, the (Z) or (E) product stream(s) with the additionalcompounds may be useful for particular applications. In otherembodiments, the product stream(s) with the additional compounds may bediscarded, a portion of the product stream(s) with the additionalcompounds may be recycled into the feed stream for one of theisomerization methods, and/or a portion of the product stream(s) may besent to an additional unit operation that will separate the 1233zd fromone or all of the additional compounds. In other embodiments, theadditional compounds may have properties that differ from both the1233zd(Z) and the 1233zd(E), allowing the 1233zd(Z), the 1233zd(E) andthe additional compounds to be separated into three or more productstreams.

Further, in certain methods of producing 1233zd, the product streamincludes both the (Z) and (E) isomers along with byproducts andunreacted materials. In certain such embodiments, a separation operation(e.g., a distillation operation) is used to separate the (Z) and (E)product streams from one another, but many of the byproducts andunreacted materials have boiling points and/or other properties thatcause at least a portion of the byproducts and unreacted materials to becaptured in one of the product streams, for example in the 1233zd(E)product stream. In such embodiments, the 1233zd(E) product stream may becaptured for other uses, and the pure or substantially pure 1233zd(Z)product stream may be used as the feed stream for one of theisomerization methods described above in order to produce a productstream consisting essentially of a mixture of (E) and 1233zd(Z). Asdescribed above, the product stream from the isomerization method maythen be fed into a separation process in order to yield separate productstreams for the (Z) and (E) isomers.

In certain embodiments, a 1233zd production operation is connecteddirectly or indirectly with a first separation operation to separate the(Z) isomer, the (E) isomer and the byproducts and unreacted materials.The first separation operation may be directly or indirectly connectedwith an isomerization operation, which in turn may be directly orindirectly connected with a second separation operation. As used herein,“indirectly connected” includes both being connected via another unitoperation as well as embodiments in which the product stream is storedfor a time prior to being fed to the next operation.

EXAMPLES

The following examples are provided for the purpose of illustrating thepresent invention but without limiting the scope thereof.

Example 1

99.9% pure 1233zd(E) was fed into Inconel 625 reactor packed withInconel 625 mesh (ID=¾ inch, L=31 inch) at the rate of 15 g/hr. Thereactor was equipped with a multi point thermocouple positioned in thecenter of the reactor and a vaporizer installed at the inlet of thereactor. The isomerization reaction was carried out at the reactiontemperatures between 355 and 449° C. The reaction products were sampledand analyzed by GC. The results are presented in Table 1 below.

TABLE 1 1233zd(E) isomerization results in Inconel 625 with Inconel 625mesh selectivity to Reaction 1233zd(E) 1233zd(Z) 1233zd(Z) Conversion ofTemp (° C.) (%) (%) (%) 1233zd(E) (%) 355 98.002 1.886 94.42%  2.00% 40096.600 3.286 96.65%  3.40% 449 87.971 11.685 97.15% 12.03%

Example 2

99.9% pure 1233zd(E) was fed into empty Inconel 625 reactor (ID=¾ in,L=31 in) at the rate of 15 g/hr. The reactor was equipped with a multipoint thermocouple positioned in the center of the reactor and avaporizer installed at the inlet of the reactor. The isomerizationreaction was carried out at the reaction temperatures between 400 and450° C. The reaction products were sampled and analyzed by GC. Theresults are presented in Table 2 below.

TABLE 2 1233zd(E) isomerization in empty Inconel 625 factor selectivityof Reaction 1233zd(E) 1233zd(Z) 1233zd(Z) Conversion of Temp (° C.) (%)(%) (%) 1233zd(E) (%) 400 96.723 3.113 94.98%  3.28% 450 88.328 11.27196.56% 11.67%

Example 3

99.9% pure 1233zd(E) was fed into Monel 400 reactor packed with Monel400 mesh(ID=¾ inch, L=31 inch) at the rate of 15 g/hr. The reactor wasequipped with a multi point thermocouple positioned in the center of thereactor and a vaporizer installed at the inlet of the reactor. Theisomerization reaction was carried out at the reaction temperatures of400° C. and 450° C. The reaction products were sampled and analyzed byGC. The results are presented in Table 3 below.

TABLE 3 1233zd(E) isomerization in Monel 400 reactor packed with Monel400 mesh selectivity to Reaction 1233zd(E) 1233zd(Z) 1233zd(Z)Conversion of Temp (° C.) (%) (%) (%) 1233zd(E) (%) 400 95.359 4.51497.27%  4.64% 450 87.778 11.812 96.65% 12.22%

Example 4

99.9% pure 1233zd(E) was fed into Inconel 625 reactor packed withStainless Steel packing (ID=¾ inch, L=31 inch, packing size 0.25 in) atthe rate of 15 g/hr. The reactor was equipped with a multi pointthermocouple positioned in the center of the reactor and a vaporizerinstalled at the inlet of the reactor. The isomerization reaction wascarried out at the reaction temperatures between 400 and 450° C. Thereaction products were sampled and analyzed by GC. The results arepresented in Table 4 below.

TABLE 4 1233zd(E) isomerization in Inconel 625 reactor packed withStainless Steel packing selectivity to Conversion of Reaction 1233zd(E)1233zd(Z) 1233zd(Z) 1233zd(E) Temp (° C.) (%) (%) (%) (%) 400 88.78810.961 97.76% 11.21% 425 85.089 14.441 96.85% 14.91% 450 85.239 14.07695.36% 14.76%

Comparative Example 1

Conversion of 1233zd(E) into 1233zd(Z) was performed using a Inconel 625reactor (ID ¾ inch, length 31 inch) equipped with a vaporizer. Thereactor was filled with 40 mL of pelletized fluorinated crystallineCr₂O₃ catalyst positioned in the middle portion of the reactor. Nickelmesh was placed at the top and at the bottom of reactor to support thecatalyst. A multi-point thermocouple was inserted at the center of thereactor. 99.9% pure 1233zd(E) was introduced into the reactor at therate of 15 g/hr. The reactor temperature for this experiment wascontrolled in the range 225-400° C. The temperature gradient throughoutthe reactor never exceeded 3-5° C. Samples of reaction products weretaken every hour and GC analysis of those samples is given in Table 5below.

TABLE 5 selectivity Conversion Reaction to of Temperature 1233zd(E)1233zd(Z) 1233zd(Z) 1233zd(E) (° C.) (%) (%) (%) (%) 225 90.292 8.62588.84 9.71 250 89.851 8.830 87.00 10.15 275 89.127 9.272 85.28 10.87 30088.317 9.692 82.96 11.68 350 85.932 10.941 77.78 14.07 400 84.614 11.70876.10 15.39

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The preceding preferred specific embodiments are,therefore, to be construed as merely illustrative, and not limitative ofthe remainder of the disclosure in any way whatsoever. In the foregoing,all temperatures are set forth uncorrected in degrees Celsius and, allparts and percentages are by weight, unless otherwise indicated.

From the foregoing description, one skilled in the art can ascertain theessential characteristics of this invention and, without departing fromthe spirit and scope thereof, can make various changes and modificationsof the invention to adapt it to various usages and conditions.

What is claimed is:
 1. A method of converting(E)1-chloro-3,3,3-trifluoropropene into(Z)1-chloro-3,3,3-trifluoropropene, comprising: providing a reactionmixture comprising (E)1-chloro-3,3,3-trifluoropropene and, optionally,(Z)-1-chloro-3,3,3-trifluoropropene; heating said reaction mixture totemperature of greater than 400° C. for a period of time and underconditions effective to form a product mixture comprising aconcentration of (Z)1-chloro-3,3,3-trifluoropropene that is greater thanthat provided in the reaction mixture.
 2. The method of claim 1, whereinsaid reaction mixture is heated to a temperature from greater than 400°C. to about 550° C.
 3. The method of claim 1, wherein said reactionmixture is heated to a temperature from greater than 400° C. to about500° C.
 4. The method of claim 1, wherein said reaction mixture isheated to a temperature from greater than 400° C. to about 475° C. 5.The method of claim 1, wherein said reaction mixture is heated to atemperature from greater than 400° C. to about 450° C.
 6. The method ofclaim 1, further comprising the step of providing a temperaturecontrolled reaction vessel that includes an interior surface, a firstopening, a second opening, a pathway fluidly connecting the first andsecond openings, and a packing material disposed in the pathway.
 7. Themethod of claim 1, further comprising vaporizing the reaction mixturebefore the heating step.
 8. The method of claim 1, further comprisingvaporizing the reaction mixture during the heating step.
 9. The methodof claim 1, wherein the reaction mixture comprises(E)1-chloro-3,3,3-trifluoropropene and(Z)1-chloro-3,3,3-trifluoropropene.
 10. The method of claim 9, whereinthe (Z)1-chloro-3,3,3-trifluoropropene is provided in the reactionmixture in an amount of less than 5 wt. %, based on the total weight ofthe reaction mixture.
 11. The method of claim 1, wherein sufficient(E)1-chloro-3,3,3-trifluoropropene is converted to(Z)1-chloro-3,3,3-trifluoropropene to yield a product mixture havingmore than 5 wt % (Z)1-chloro-3,3,3-trifluoropropene, based on the totalweight of the product mixture.
 12. The method of claim 1, wherein theproduct mixture has between about 5 wt % and about 20 wt %(Z)-1-chloro-3,3,3-trifluoropropene, based on the total weight of theproduct mixture.
 13. The method of claim 6, wherein at least a portionof the reaction mixture is heated by an outer surface of the packingmaterial.
 14. The method of claim 13, wherein the packing material hascatalytic properties.
 15. The method of claim 14, wherein the packingmaterial comprises a stainless steel, nickel or nickel-basedcomposition.
 16. The method of claim 14, wherein the packing materialcomprises a nickel-based alloy.
 17. The method of claim 1, wherein theproduct mixture consists essentially of(E)-1-chloro-3,3,3-trifluoropropene and(Z)1-chloro-3,3,3-trifluoropropene.
 18. The method of claim 1, whereinthe method of converting is reagent-free.